U.S. patent number 7,034,174 [Application Number 10/314,939] was granted by the patent office on 2006-04-25 for mono-, oligo- and polymers comprising a 2,6-azulene group and their use as charge transport materials.
This patent grant is currently assigned to MERCK Patent GmbH. Invention is credited to Louise Diane Farrand, Michael Findlater, Mark Giles, Martin Heeney, Iain McCulloch, Maxim Shkunov, David Sparrowe, Marcus Thompson, Steven Tierney.
United States Patent |
7,034,174 |
Farrand , et al. |
April 25, 2006 |
**Please see images for:
( Certificate of Correction ) ** |
Mono-, oligo- and polymers comprising a 2,6-azulene group and their
use as charge transport materials
Abstract
Conjugated mono-, oligo- and polyazulenes are suitable for use
as semiconductors or charge transport materials in optical,
electrooptical or electronic devices including field effect
transistors, electroluminescent, photovoltaic and sensor devices,
and as field effect transistors and semi-conducting components.
Inventors: |
Farrand; Louise Diane
(Spetisbury, Blandford Forum, GB), Findlater; Michael
(Glasgow, GB), Giles; Mark (Southampton,
GB), Heeney; Martin (Southampton, GB),
Tierney; Steven (Southampton, GB), Thompson;
Marcus (Fordingbridge, GB), Shkunov; Maxim
(Southampton, GB), Sparrowe; David (Southbourne,
GB), McCulloch; Iain (Kings Somborne, GB) |
Assignee: |
MERCK Patent GmbH (Darmstadt,
DE)
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Family
ID: |
8179477 |
Appl.
No.: |
10/314,939 |
Filed: |
December 10, 2002 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20030122479 A1 |
Jul 3, 2003 |
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Foreign Application Priority Data
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Dec 10, 2001 [EP] |
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01129216 |
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Current U.S.
Class: |
556/400;
430/58.05; 558/248; 558/265; 564/439; 568/38; 568/632 |
Current CPC
Class: |
C07C
13/52 (20130101); C08G 61/02 (20130101); C08G
61/10 (20130101); C09K 11/06 (20130101); H01B
1/124 (20130101); H01B 1/127 (20130101); H01L
51/0035 (20130101); H01L 51/0057 (20130101); H01L
51/0058 (20130101); C09K 2211/1416 (20130101); Y02E
10/549 (20130101); C07C 2602/30 (20170501) |
Current International
Class: |
C07F
7/02 (20060101) |
Field of
Search: |
;313/504 ;556/400
;558/248,265 ;560/76 ;564/439 ;568/38,632 ;428/690 ;569/76 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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34 25 511 |
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Jan 1986 |
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DE |
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39 29 383 |
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Mar 1991 |
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DE |
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39 38 094 |
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May 1991 |
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DE |
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44 45 619 |
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Jun 1996 |
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DE |
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0 187 015 |
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Jul 1986 |
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EP |
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0 187 015 |
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Jul 1986 |
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EP |
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0 528 662 |
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Feb 1993 |
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EP |
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0 528 662 |
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Feb 1993 |
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EP |
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1 256 602 |
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Nov 2002 |
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EP |
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96/21659 |
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Jul 1996 |
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WO |
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WO 97 00600 |
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Jan 1997 |
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WO |
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00/79617 |
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Dec 2000 |
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WO |
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Other References
Balschukat et al., Novel 2, 6-Disubstituted azulenes, Chemische
Berichte (1986), 119 (7), 2272-2288. cited by examiner .
Kato et al., Synthesis of anti-[2,2] (2,6) Azulenophane from
5-methyltropolone, Tetrahedron Letters (1976), (24), 2045-2048.
cited by examiner .
Keehn et al., Cyclophanes V. Anti-[2.2] (2,6) Azulenophane,
Tetrehedron Letters No. 14. pp. 1043-4046, 1976. cited by examiner
.
Daub et al., Azulene Appended Cellulose: Synthesis, Optional and
Chiroptical Properties, Film Formation by Electrochemical
Oxidation, Macromol. Chem. Phys. 2000, 201, 2091-2100. cited by
examiner .
European International Search Report dated Mar. 10, 2003. cited by
other .
Patent Abstract of Japan No. 02-069441 dated Mar. 8, 1990. cited by
other .
Patent Abstract of Japan No. 02-069437 dated May 29, 1990. cited by
other .
Patent Abstract of Japan No. 03-122189 dated May 24, 1991. cited by
other .
Patent Abstract of Japan No. 02-069439 dated Mar. 8, 1990. cited by
other .
Patent Abstract of Japan No. 02-069438 dated Mar. 8, 1990. cited by
other .
Patent Abstract of Japan No. 60-104180 dated Jun. 8, 1985. cited by
other .
S.E. Estdale et al., "The Azulene Ring as a 1-10 Structural Element
in Liquid Crystals", Journal of Materials Chemistry, vol. 7, No. 3,
(1997), pp. 391-401. cited by other.
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Primary Examiner: Richter; Johann
Assistant Examiner: Nwaonicha; Chukwuma
Attorney, Agent or Firm: Millen White Zelano & Branigan,
P.C.
Claims
The invention claimed is:
1. A mono-, oligo- or polymeric compound comprising one or more
identical or different recurring units of formula I
-[(A).sub.a-(B).sub.b-(C).sub.c]- I wherein A and C are
independently of each other and independently in each occurrence
--CX.sup.1.dbd.CX.sup.2--, --C.ident.C--, optionally substituted
arylene, optionally substituted heteroarylene, or is substituted or
unsubstituted azulene-2,6-diyl, [2,6']-bisazulene-6,2'-diyl,
[2,2']-bisazulene-6,6'-diyl, [6,6']-bisazulene-2,2'-diyl, or a
mirror image of one of these groups, X.sup.1 and X.sup.2 are
independently of each other H, F, Cl or CN, B is independently in
each occurrence azulene-2,6-diyl, [2,6']-bisazulene-6,2'-diyl,
[2,2']-bisazulene-6,6'-diyl, [6,6']-bisazulene-2,2'-diyl, all of
which are substituted or unsubstituted, or a mirror image of one of
these groups, and a, b and c are independently of each other 0, 1,
2 or 3, with a+b+c>0, with the proviso that the mono-, oligo- or
polymer comprises at least two azulene-2,6-diyl groups or at least
one [2,6']-bisazulene-6,2'-diyl, [2,2']-bisazulene-6,6'-diyl or
[6,6']-bisazulene-2,2'-diyl group.
2. A compound according to claim 1, wherein A and C are
independently of each other and independently in each occurrence
--CX.sup.1.dbd.CX.sup.2--; --C.ident.C--; a mono-, bi- or tricyclic
aromatic or heteroaromatic group with up to 25 C atoms that is
optionally substituted with one or more groups selected from H,
halogen and straight chain, branched or cyclic alkyl with 1 to 20
C-atoms, which is unsubstituted, mono- or poly-substituted by F,
Cl, Br, I or CN, and in which one or more non-adjacent CH.sub.2
groups are optionally replaced, in each case independently from one
another, by --O--, --S--, --NH--, --NR.sup.0--,
--SiR.sup.0R.sup.00--, --CO--, --COO--, --OCO--, --OCO--O--,
--S--CO--, --CO--S--, --CH.dbd.CH-- or --C.ident.C-- in such a
manner that O and/or S atoms are not linked directly to one
another; azulene-2,6-diyl or a mirror image thereof;
[2,6']-bisazulene-6,2'-diyl or a mirror image thereof;
[2,2']-bisazulene-6,6'-diyl or a mirror image thereof; or
[6,6']-bisazulene-2,2'-diyl or a mirror image thereof.
3. A compound according to claim 1, wherein said compound is
selected of formula I1
R.sup.6-[(A).sub.a-(B).sub.b-(C).sub.c].sub.n-R.sup.2 I1 wherein B
is independently in each occurrence selected from formulae IIa to
IId and their mirror images ##STR00010## R.sup.1 to R.sup.8 are
independently of each other H, halogen, straight chain, branched or
cyclic alkyl with 1 to 20 C-atoms, which is unsubstituted, mono- or
poly-substituted by F, Cl, Br, I or CN, and in which one or more
non-adjacent CH.sub.2 groups are optionally replaced, in each case
independently from one another, by --O--, --S--, --NH--,
--NR.sup.0--, --SiR.sup.0R.sup.00--, --CO--, --COO--, --OCO--,
--OCO--O--, --S--CO--, --CO--S--, --CH.dbd.CH-- or --C.ident.C-- in
such a manner that O and/or S atoms are not linked directly to one
another, optionally substituted aryl, or optionally substituted
heteroaryl, R.sup.0 and R.sup.00 are independently of each other H
or alkyl with 1 to 12 C-atoms, n is an integer from 1 to 5000,
wherein the recurring units [(A).sub.a-(B).sub.b-(C).sub.c] can be
identical or different.
4. A compound according to claim 3, wherein R.sup.1 to R.sup.8 are
independently of each other H; halogen; straight chain, branched or
cyclic alkyl with 1 to 20 C-atoms, which is unsubstituted, mono- or
poly-substituted by F, Cl, Br, I or CN, and in which one or more
non-adjacent CH.sub.2 groups are optionally replaced, in each case
independently from one another, by --O--, --S--, --NH--,
--NR.sup.0--, --SiR.sup.0R.sup.00--, --CO--, --COO--, --OCO--,
--OCO--O--, --S--CO--, --CO--S--, --CH.dbd.CH-- or --C.ident.C-- in
such a manner that O and/or S atoms are not linked directly to one
another; or a mono-, bi- or tricyclic aromatic or heteroaromatic
group with up to 25 C atoms that is optionally substituted with one
or more groups selected from H, halogen and straight chain,
branched or cyclic alkyl with 1 to 20 C-atoms, which is
unsubstituted, mono- or poly-substituted by F, Cl, Br, I or CN, and
in which one or more non-adjacent CH.sub.2 groups are optionally
replaced, in each case independently from one another, by --O--,
--S--, --NH--, --NR.sup.0--, --SiR.sup.0R.sup.00--, --CO--,
--COO--, --OCO--, --OCO--O--, --S--CO--, --CO--S--, --CH.dbd.CH--
or --C.ident.C-- in such a manner that O and/or S atoms are not
linked directly to one another.
5. A compound according to claim 1, wherein n is an integer from 2
to 5000.
6. A compound according to claim 3, wherein n is an integer from 2
to 5000.
7. A compound according to claim 3, wherein R.sup.1, R.sup.3,
R.sup.4, R.sup.5, R.sup.7 and R.sup.8 are selected from H, C.sub.1
C.sub.20-alkyl, C.sub.1 C.sub.20-alkyl substituted with one or more
fluorine atoms, C.sub.1 C.sub.20-alkenyl, C.sub.1 C.sub.20-alkynyl,
C.sub.1 C.sub.20-alkoxy, C.sub.1 C.sub.20-thioether, C.sub.1
C.sub.20-silyl, C.sub.1 C.sub.20-ester, C.sub.1 C.sub.20-amino,
C.sub.1 C.sub.20-fluoroalkyl, optionally substituted aryl, or
optionally substituted heteroaryl.
8. A compound according to claim 6, wherein R.sup.1, R.sup.3,
R.sup.4, R.sup.5, R.sup.7 and R.sup.8 are selected from H, C.sub.1
C.sub.20-alkyl, C.sub.1 C.sub.20-alkyl substituted with one or more
fluorine atoms, C.sub.1 C.sub.20-alkenyl, C.sub.1 C.sub.20-alkynyl,
C.sub.1 C.sub.20-alkoxy, C.sub.1 C.sub.20-thioether, C.sub.1
C.sub.20-silyl, C.sub.1 C.sub.20-ester, C.sub.1 C.sub.20-amino,
C.sub.1 C.sub.20-fluoroalkyl, optionally substituted aryl, or
optionally substituted heteroaryl.
9. A compound according to claim 3, wherein R.sup.2 and R.sup.6 are
each selected from C.sub.1 C.sub.20-alkyl, C.sub.1 C.sub.20-alkyl
substituted with one or more fluorine atoms, C.sub.1
C.sub.20-alkenyl, C.sub.1 C.sub.20-alkynyl, C.sub.1
C.sub.20-alkoxy, C.sub.1 C.sub.20-thioether, C.sub.1
C.sub.20-silyl, C.sub.1 C.sub.20-ester, C.sub.1 C.sub.20-amino,
C.sub.1 C.sub.20-fluoroalkyl, optionally substituted aryl, or
optionally substituted heteroaryl.
10. A compound according to claim 6, wherein R.sup.2 and R.sup.6
are each selected from C.sub.1 C.sub.20-alkyl, C.sub.1
C.sub.20-alkyl substituted with one or more fluorine atoms, C.sub.1
C.sub.20-alkenyl, C.sub.1 C.sub.20-alkynyl, C.sub.1
C.sub.20-alkoxy, C.sub.1 C.sub.20-thioether, C.sub.1
C.sub.20-silyl, C.sub.1 C.sub.20-ester, C.sub.1 C.sub.20-amino,
C.sub.1 C.sub.20-fluoroalkyl, optionally substituted aryl, or
optionally substituted heteroaryl.
11. A compound according to claim 7, wherein R.sup.2 and R.sup.6
are each selected from C.sub.1 C.sub.20-alkyl, C.sub.1
C.sub.20-alkyl substituted with one or more fluorine atoms, C.sub.1
C.sub.20-alkenyl, C.sub.1 C.sub.20-alkynyl, C.sub.1
C.sub.20-alkoxy, C.sub.1 C.sub.20-thioether, C.sub.1
C.sub.20-silyl, C.sub.1 C.sub.20-ester, C.sub.1 C.sub.20-amino,
C.sub.1 C.sub.20-fluoroalkyl, optionally substituted aryl, or
optionally substituted heteroaryl.
12. A compound according to claim 8, wherein R.sup.2 and R.sup.6
are each selected from C.sub.1 C.sub.20-alkyl, C.sub.1
C.sub.20-alkyl substituted with one or more fluorine atoms, C.sub.1
C.sub.20-alkenyl, C.sub.1 C.sub.20-alkynyl, C.sub.1
C.sub.20-alkoxy, C.sub.1 C.sub.20-thioether, C.sub.1
C.sub.20-silyl, C.sub.1 C.sub.20-ester, C.sub.1 C.sub.20-amino,
C.sub.1 C.sub.20-fluoroalkyl, optionally substituted aryl, or
optionally substituted heteroaryl.
13. A compound according to claim 3, wherein said compound is
selected from the following formulae ##STR00011## ##STR00012##
##STR00013## wherein Ar is (ar).sub.m, ar is arylene or
heteroarylene, m is 1, 2 or 3, and Z.sup.1, Z.sup.2 and Z.sup.3 are
independently of each other --CX.sup.1.dbd.CX.sup.2--, C.ident.C--
or a single bond.
14. A compound according to claim 1, wherein said compound is
oxidatively or reductively doped to form conducting ionic species.
Description
FIELD OF INVENTION
The invention relates to new conjugated mono-, oligo- and
polyazulenes. The invention further relates to their use as
semiconductors or charge transport materials in optical,
electrooptical or electronic devices including field effect
transistors, electroluminescent, photovoltaic and sensor devices.
The invention further relates to field effect transistors and
semi-conducting components comprising the new mono-, oligo- and
polyazulenes.
BACKGROUND AND PRIOR ART
Organic materials have recently shown promise as the active layer
in organic based thin film transistors and organic field effect
transistors [see H. E. Katz, Z. Bao and S. L. Gilat, Acc. Chem.
Res., 2001, 34, 5, 359]. Such devices have potential applications
in smart cards, security tags and the switching element in flat
panel displays. Organic materials are envisaged to have substantial
cost advantages over their silicon analogues if they can be
deposited from solution, as this enables a fast, large-area
fabrication route.
The performance of the device is principally based upon the charge
carrier mobility of the semi-conducting material and the current
on/off ratio, so the ideal semi-conductor should have a low
conductivity in the off state, combined with a high charge carrier
mobility (>1.times.10.sup.-3 cm.sup.2 V.sup.-1 s.sup.-1). In
addition, it is important that the semi-conducting material is
relatively stable to oxidation, i.e., it has a high ionisation
potential, as oxidation leads to reduced device performance.
A known compound which has been shown to be an effective p-type
semiconductor for OFETs is pentacene [see S. F. Nelson, Y. Y. Lin,
D. J. Gundlach and T. N. Jackson, Appl. Phys. Lett., 1998, 72,
1854]. When deposited as a thin film by vacuum deposition, it was
shown to have carrier mobilities in excess of 1 cm.sup.2 V.sup.-1
s.sup.-1 with very high current on/off ratios greater than
10.sup.6. However, vacuum deposition is an expensive processing
technique that is unsuitable for the fabrication of large-area
films.
It is an aim of the present invention to provide new materials for
use as semiconductors or charge transport materials, which are easy
to synthesise, have high charge mobility, good processability and
improved oxidative stability. Other aims of the invention are
immediately evident to those skilled in the art from the following
description.
The inventors have found that these aims can be achieved by
providing new monomers, oligomers and polymers based on
azulene.
##STR00001##
Azulene is a non-benzenoid aromatic hydrocarbon which is planar and
thermodynamically stable. Polymerisation at the 2- or 6-position
results in a linear structure. As a result, polyazulenes pack
closely, thus exhibiting a higher degree of order that leads to
particularly high charge carrier mobility. Furthermore, by adding
alkyl chains and other substituent groups to the azulene core, the
azulenes can be made more soluble thus being suitable for spin
coating or solution coating techniques, rather than vacuum
deposition, to prepare thin films for use, e.g., in electronic
devices such as transistors.
1,3-Polyazulenes (A) have been prepared electrochemically, as
reported by K. Iwasaki et al, Synth. Metals, 1995, 69, 543 and Y-B.
Shim et al, J. Electrochem. Soc., 1997, 144, 3027 and M. Porsch et
al in Adv. Mater., 1997, 9, 635, and by stirring in strong acid, as
reported by N. Kihara et al, J. Amer. Chem. Soc., 1997, 30, 6385.
Azulene appended cellulose has also been reported [see F. X. Redl
et al, Macromol. Chem. Phys., 2000, 201, 2091]
##STR00002##
Copolymers of azulene have also been reported. DE 34 25 511, DE
3929383 and DE 39 38 094 disclose a copolymerisate of pyrrole and
azulene obtained by electrochemical polymerisation in the presence
of sulfonic acid and a conducting salt. DE 44 45 619 discloses a
copolymer with azulene and phenylene units linked by
phenylmethylene groups.
However, polyazulenes polymerised at the 2- and 6-position
according to the present invention have not been reported.
Another aspect of the present inventions relates to advantageous
uses of the mono-, oligo- and polyazulenes, including their
oxidatively or reductively doped forms, according to the
invention.
DEFINITION OF TERMS
The term `film` includes self-supporting, i.e., free-standing,
films that show more or less pronounced mechanical stability and
flexibility, as well as coatings or layers on a supporting
substrate or between two substrates.
SUMMARY OF THE INVENTION
One object of the invention is to provide mono-, oligo- and
polymers comprising at least two azulene-2,6-diyl groups.
Another object of the invention is the use of mono-, oligo- and
polyazulenes according to the invention as semiconductors or charge
transport materials, in particular in optical, electrooptical or
electronic devices, like, for example, components of integrated
circuitry, field effect transistors (FET), for example, as thin
film transistors in flat panel display applications or for Radio
Frequency Identification (RFID) tags, or in semiconducting
components for organic light emitting diode (OLED) applications
such as electroluminescent displays or backlights of, e.g., liquid
crystal displays, for photovoltaic or sensor devices, as electrode
materials in batteries, as photoconductors and for
electrophotographic applications like electrophotographic
recording.
Another object of the invention is to provide a field effect
transistor, for example, as a component of integrated circuitry, as
a thin film transistor in flat panel display applications, or in a
Radio Frequency Identification (RFID) tag, comprising one or more
mono-, oligo- or polyazulenes according to the invention.
Another object of the invention is to provide a semi-conducting
component, for example in OLED applications like electroluminescent
displays or backlights of, e.g., liquid crystal displays, in
photovoltaic or sensor devices, as electrode materials in
batteries, as photoconductors and for electrophotographic
applications, comprising one or more mono-, oligo- or polymers
according to the invention.
Another object of the invention is to provide a security marking or
device comprising an RFID or ID tag or a FET according to the
invention.
Upon further study of the specification and appended claims,
further objects and advantages of this invention will become
apparent to those skilled in the art.
DETAILED DESCRIPTION OF THE INVENTION
The mono-, oligo- and polyazulenes according to the present
invention are especially useful as charge transport semiconductors
in that they have high carrier mobilities. Particularly preferred
are mono-, oligo- and polyazulenes wherein the azulene group is
substituted by one or more alkyl or fluoroalkyl groups. The
introduction of alkyl side chains to the azulene group and attached
rings improves the solubility and therefore the solution
processibility of the inventive materials.
Especially preferred are mono-, oligo- and polymers comprising one
or more identical or different recurring units of formula I
-[(A).sub.a-(B).sub.b-(C).sub.c]- I wherein A and C are
independently of each other and independently in each occurrence
--CX.sup.1.dbd.CX.sup.2--, --C.ident.C--, or optionally substituted
arylene or heteroarylene, or have one of the meanings of B, X.sup.1
and X.sup.2 are independently of each other H, F, Cl or CN, B is
independently in each occurrence azulene-2,6-diyl,
[2,6']-bisazulene-6,2'-diyl, [2,2']-bisazulene-6,6'-diyl,
[6,6']-bisazulene-2,2'-diyl, all of which are substituted or
unsubstituted, or a mirror image of one of these groups, and a, b
and c are independently of each other 0, 1, 2 or 3, e.g., 0, 1 or
2, with a+b+c>0, with the proviso that the mono-, oligo- and
polyazulenes comprise at least two azulene-2,6-diyl groups or at
least one [2,6']-bisazulene-6,2'-diyl, [2,2']-bisazulene-6,6'-diyl
or [6,6']-bisazulene-2,2'-diyl group.
In the oligo- and polymers of the present invention the recurring
units (A).sub.a-(B).sub.b-(C).sub.c in case of multiple occurrence
can be selected of formula I independently of each other, so that
an oligo- or polymer may comprise identical or different recurring
units (A).sub.a-(B).sub.b-(C).sub.c. The oligo- and polymers thus
include homopolymers and copolymers like for example statistically
random copolymers, for example with a monomer sequence such as
-A-B-C-C-B-A-B-, alternating copolymers, for example with a monomer
sequence such as -A-B-C-A-B-C-, and block copolymers, for example
with a monomer sequence such as -A-A-B-B-B-B-C-C-C-, wherein the
groups A and C preferably form a conjugated system together with
the group B.
Further preferred are mono-, oligo- and polymers comprising one or
more recurring units (A).sub.a-(B).sub.b-(C).sub.c, wherein a=c=0
and b=1, very preferably consisting exclusively of such recurring
units.
Further preferred are mono-, oligo- and polymers comprising one or
more recurring units (A).sub.a-(B).sub.b-(C).sub.c, wherein b=c=1
and a=0, very preferably consisting exclusively of such recurring
units.
Further preferred are mono-, oligo- and polymers comprising one or
more recurring units (A).sub.a-(B).sub.b-(C).sub.c, wherein
a=b=c=1, very preferably consisting exclusively of such recurring
units.
Especially preferred are mono-, oligo- and polymers of formula I1
R.sup.6-[(A).sub.a-(B).sub.b-(C).sub.c].sub.n-R.sup.2 I1 wherein A,
C, a, b and c are as defined in formula I, B is independently in
each occurrence a group selected of formulae IIa to IId or their
mirror images
##STR00003## R.sup.1 to R.sup.8 are independently of each other H,
halogen or straight chain, branched or cyclic alkyl with 1 to 20
C-atoms, which is unsubstituted, mono- or poly-substituted by F,
Cl, Br, I or CN, and in which one or more non-adjacent CH.sub.2
groups are optionally replaced, in each case independently from one
another, by --O--, --S--, --NH--, --NR.sup.0--,
--SiR.sup.0R.sup.00--, --CO--, --COO--, --OCO--, --OCO--O--,
--S--CO--, --CO--S--, --CH.dbd.CH-- or --C.ident.C-- in such a
manner that O and/or S atoms are not linked directly to one
another, or optionally substituted aryl or heteroaryl, R.sup.0 and
R.sup.00 are independently of each other H or alkyl with 1 to 12
C-atoms, n is an integer from 1 to 5000, wherein the recurring
units [(A).sub.a-(B).sub.b-(C).sub.c] can be identical or
different.
Especially preferred are mono-, oligo- and polymers of formula I1
wherein n is an integer from 2 to 5000, in particular from 20 to
1000, n is an integer from 2 to 5, the molecular weight is from
5000 to 100000, R.sup.1, R.sup.3, R.sup.4, R.sup.5, R.sup.7 and
R.sup.8 are each independently selected from H, C.sub.1
C.sub.20-alkyl that is optionally substituted with one or more
fluorine atoms, C.sub.1 C.sub.20-alkenyl, C.sub.1 C.sub.20-alkynyl,
C.sub.1 C.sub.20-alkoxy, C.sub.1 C.sub.20-thioether, C.sub.1
C.sub.20-silyl, C.sub.1 C.sub.20-ester, C.sub.1 C.sub.20-amino,
C.sub.1 C.sub.20-fluoroalkyl, and optionally substituted aryl or
heteroaryl, R.sup.2 and R.sup.6 are each independently selected
from C.sub.1 C.sub.20-alkyl that is optionally substituted with one
or more fluorine atoms, C.sub.1 C.sub.20-alkenyl, C.sub.1
C.sub.20-alkynyl, C.sub.1 C.sub.20-alkoxy, C.sub.1
C.sub.20-thioether, C.sub.1 C.sub.20-silyl, C.sub.1 C.sub.20-ester,
C.sub.1 C.sub.20-amino, C.sub.1 C.sub.20-fluoroalkyl, and
optionally substituted aryl or heteroaryl, A and C are each
independently optionally substituted arylene or heteroarylene, A
and C are each independently --CX.sup.1.dbd.CX.sup.2-- or
--C.ident.C--, in at least one monomer unit
(A).sub.a-(B).sub.b-(C).sub.c a, b and c are 1, and one of A and C
is arylene or heteroarylene and the other is
--CX.sup.1.dbd.CX.sup.2-- or --C.ident.C--, n>1.
Especially preferred are mono-, oligo- and polymers of the
following formulae
##STR00004## ##STR00005## ##STR00006## wherein R.sup.1 to R.sup.8
and n have the meanings given in formula I1, Ar is (ar).sub.m, with
ar being arylene or heteroarylene and m being 1, 2 or 3, Z.sup.1,
Z.sup.2 and Z.sup.3 are independently of each other
--CX.sup.1.dbd.CX.sup.2--, --C.ident.C-- or a single bond, and
X.sup.1 and X.sup.2 have the meanings given in formula I.
In these preferred formulae, R.sup.1, R.sup.3, R.sup.4, R.sup.5,
R.sup.7 and R.sup.8 are very preferably F or alkyl with 1 to 16
C-atoms that is optionally fluorinated, R.sup.2 and R.sup.6 are
very preferably H, halogen or alkyl with 1 16 C atoms that is
optionally fluorinated, ar is very preferably 1,4-phenylene,
alkoxyphenylene, alkylfluorene, thiophene-2,5-diyl,
thienothiophene-2,5-diyl or dithienothiophene-2,6-diyl, m is
preferably 1, n is preferably an integer from 2 to 5000, in
particular from 20 to 1000.
In the formulae shown above and below, aryl and heteroaryl
preferably denote a mono-, bi- or tricyclic aromatic or
heteroaromatic group with up to 25 C atoms that optionally
comprises fused rings and is optionally substituted with one or
more groups selected from H, halogen and straight chain, branched
or cyclic alkyl with 1 to 20 C-atoms, which is unsubstituted, mono-
or poly-substituted by F, Cl, Br, I or CN, and in which one or more
non-adjacent CH.sub.2 groups are optionally replaced, in each case
independently from one another, by --O--, --S--, --NH--,
--NR.sup.0--, --SiR.sup.0R.sup.00--, --CO--, --COO--, --OCO--,
--OCO--O--, --S--CO--, --CO--S--, --CH.dbd.CH-- or --C.ident.C-- in
such a manner that O and/or S atoms are not linked directly to one
another.
Especially preferred aryl and heteroaryl groups are phenyl in
which, in addition, one or more CH groups are optionally replaced
by N, naphthalene, thiophene, thienothiophene, dithienothiophene,
alkyl fluorene and oxazole, all of which are unsubstituted, mono-
or polysubstituted with L, wherein L is halogen or an alkyl,
alkoxy, alkylcarbonyl or alkoxycarbonyl group with 1 to 12 C atoms,
wherein one or more H atoms are optionally replaced by F or Cl.
Arylene and heteroarylene preferably denote a bivalent mono-, bi-
or tricyclic aromatic or heteroaromatic group with up to 25 C atoms
that optionally comprises fused rings and is optionally substituted
with one or more groups selected from H, halogen and straight
chain, branched or cyclic alkyl with 1 to 20 C-atoms, which is
unsubstituted, mono- or poly-substituted by F, Cl, Br, I or CN, and
in which one or more non-adjacent CH.sub.2 groups are optionally
replaced, in each case independently from one another, by --O--,
--S--, --NH--, --NR.sup.0--, --SiR.sup.0R.sup.00--, --CO--,
--COO--, --OCO--, --OCO--O--, --S--CO--, --CO--S--, --CH.dbd.CH--
or --C.ident.C-- in such a manner that O and/or S atoms are not
linked directly to one another.
Especially preferred arylene and heteroarylene groups are
1,4-phenylene in which, in addition, one or more CH groups are
optionally replaced by N, naphthalene-2,6-diyl, thiophene-2,5-diyl,
thienothiophene-2,5-diyl, dithienothiophene-2,6-diyl, alkyl
fluorene and oxazole, all of which are unsubstituted, mono- or
polysubstituted with L as defined above.
Further preferred aryl and heteroaryl groups include five-membered
heterocyclics like oxazole or isoxazole, N-substituted imidazole or
pyrazole, thiazole or isothiazole, oxadiazole, N-substituted
triazole, six-membered heterocyclics like pyridine, pyridazine,
pyrimidine, pyrazine, triazine and tetrazine, heterocyclics with
fused rings like benzoxazole, benzothiazole, benzimidazole,
quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline,
phthalazine, benzothiadiazole, benzotriazole, benzotriazine,
phenazine, phenanthridine, acridine, or condensed polycyclics like
acenaphthene, phenanthrene, anthracene, fluoranthene, pyrene,
perylene, rubrene, chrysene, naphthacene, coronene or triphenylene,
all of which are unsubstituted, mono- or polysubstituted with L as
defined above.
CX.sup.1.dbd.CX.sup.2 is preferably --CH.dbd.CH--, --CH.dbd.CF--,
--CF.dbd.CH--, --CF.dbd.CF--, --CH.dbd.C(CN)-- or
--C(CN).dbd.CH--.
If in the formulae shown above and below, one of R.sup.1 to R.sup.8
is an alkyl or alkoxy radical, i.e., where the terminal CH.sub.2
group is replaced by --O--, this may be straight-chain or branched.
It is preferably straight-chain, has 2 to 8 carbon atoms and
accordingly is preferably ethyl, propyl, butyl, pentyl, hexyl,
heptyl, octyl, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptoxy,
or octoxy, furthermore methyl, nonyl, decyl, undecyl, dodecyl,
tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy,
dodecoxy, tridecoxy or tetradecoxy, for example.
Oxaalkyl, i.e., where one CH.sub.2 group is replaced by --O--, is
preferably straight-chain 2-oxapropyl(=methoxymethyl),
2-(=ethoxymethyl) or 3-oxabutyl(=2-methoxyethyl), 2-, 3-, or
4-oxapentyl, 2-, 3-, 4-, or 5-oxahexyl, 2-, 3-, 4-, 5-, or
6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-,
7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl, for
example.
"Fluorinated alkyl" or "fluoroalkyl" is mono-, poly- or
perfluorinated alkyl, preferably C.sub.iF.sub.2i+1, wherein i is an
integer from 1 to 15, in particular CF.sub.3, C.sub.2F.sub.5,
C.sub.3F.sub.7, C.sub.4F.sub.9, C.sub.5F.sub.11, C.sub.6F.sub.13,
C.sub.7F.sub.15 or C.sub.8F.sub.17, very preferably
C.sub.6F.sub.13.
Halogen is preferably F or Cl.
The mono-, oligo- and polyazulenes of the present invention can be
synthesized according to or in analogy to known methods. Some
preferred methods are described below.
As shown in Scheme 1, Ullmann-type coupling (see T. Morita and K.
Takase, Bull. Chem. Soc. Jpn., 1982, 55, 1144 1152) gives biazulene
(1) followed by bromination (see T. Nozoe, T. Asao and M. Oda in
Bull. Chem. Soc. Jpn., 1974, 47, 681) gives compound (2) and
decarboxylation (see D. Balschukat and E. V. Dehmlow, Chem. Ber.,
1986, 119, 2272) gives the 2,2'-biazulene (3). Polymerisation can
proceed via conventional routes: Ni(cod).sub.2 and
triphenylphosphine (Yamamoto coupling) to yield (5). Alternatively,
(3) is converted to the mono-Grignard and polymerised using
Ni(dppp)Cl.sub.2 to yield (5). Other coupling routes are Stille
coupling (see D. Milstein and J. K. Stille, J. Am. Chem. Soc.,
1979, 101, 4992), Rieke coupling (see T.-A. Chen and R. D. Rieke,
J. Am. Chem. Soc., 1992, 114, 10087), and Suzuki coupling (see N.
Miyaura, T. Yanagi and A. Suzuki, Synth. Commun., 1981, 11,
513).
##STR00007## wherein Ar, X.sup.1, X.sup.2 and n have the meanings
given in formula I and I1.
As shown in Scheme 2, (3) can be cross-coupled under Sonogashira
conditions with 4-chlorophenylacetylene to give the 2,2' biazulene
(8), which can be polymerised under typical and known conditions to
give for example highly conjugated polymer (9).
##STR00008##
As depicted in scheme 3, compound (10) is prepared by bromination
of 2-amino-1,3-azulene diethylcarboxylate (see T. Nozoe, S. Seto
and S. Matsumara, Bull. Chem. Soc. Jpn., 1962, 35, 1990). (11) is
the cross-coupled product of (10) with protected acetylene. The
amine is converted to the chloro compound (13), decarboxylated with
acid and polymerised to give (15).
##STR00009##
A further aspect of the invention relates to both the oxidised and
reduced form of the compounds and materials according to this
invention. Either loss or gain of electrons results in formation of
a highly delocalised ionic form, which is of high conductivity.
This can occur on exposure to common dopants. Suitable dopants and
methods of doping are known to those skilled in the art, e.g., from
EP 0 528 662, U.S. Pat. No. 5,198,153 or WO 96/21659.
The doping process typically implies treatment of the semiconductor
material with an oxidating or reducing agent in a redox reaction to
form delocalised ionic centres in the material, with the
corresponding counterions derived from the applied dopants.
Suitable doping methods comprise for example exposure to a doping
vapor in the atmospheric pressure or at a reduced pressure,
electrochemical doping in a solution containing a dopant, bringing
a dopant into contact with the semiconductor material to be
thermally diffused, and ion-implantantion of the dopant into the
semiconductor material.
When electrons are used as carriers, suitable dopants are for
example halogens (e.g. I.sub.2, Cl.sub.2, Br.sub.2, ICl, ICl.sub.3,
IBr and IF), Lewis acids (e.g., PF.sub.5, AsF.sub.5, SbF.sub.5,
BF.sub.3, BCl.sub.3, SbCl.sub.5, BBr.sub.3 and SO.sub.3), protonic
acids, organic acids, or amino acids (e.g., HF, HCl, HNO.sub.3,
H.sub.2SO.sub.4, HClO.sub.4, FSO.sub.3H and ClSO.sub.3H),
transition metal compounds (e.g., FeCl.sub.3, FeOCl,
Fe(ClO.sub.4).sub.3, Fe(4-CH.sub.3C.sub.6H.sub.4SO.sub.3).sub.3,
TiCl.sub.4, ZrCl.sub.4, HfCl.sub.4, NbF.sub.5, NbCl.sub.5,
TaCl.sub.5, MoF.sub.5, MoCl.sub.5, WF.sub.5, WCl.sub.6, UF.sub.6
and LnCl.sub.3 (wherein Ln is a lanthanoid), anions (e.g.,
Cl.sup.-, Br.sup.-, I.sup.-, I.sub.3.sup.-, HSO.sub.4.sup.-,
SO.sub.4.sup.2-, NO.sub.3.sup.-, ClO.sub.4.sup.-, BF.sub.4.sup.-,
PF.sub.6.sup.-, AsF.sub.6.sup.-, SbF.sub.6.sup.-, FeCl.sub.4.sup.-,
Fe(CN).sub.6.sup.3-, and anions of various sulfonic acids, such as
aryl-SO.sub.3.sup.-). When holes are used as carriers, examples of
dopants are cations (e.g., H.sup.+, Li.sup.+, Na.sup.+, K.sup.+,
Rb.sup.+ and Cs.sup.+), alkali metals (e.g., Li, Na, K, Rb, and
Cs), alkaline-earth metals (e.g., Ca, Sr, and Ba), O.sub.2,
XeOF.sub.4, (NO.sub.2.sup.+)(SbF.sub.6.sup.-),
(NO.sub.2.sup.+)(SbCl.sub.6.sup.-),
(NO.sub.2.sup.+)(BF.sub.4.sup.-), AgClO.sub.4, H.sub.2IrCl.sub.6,
La(NO.sub.3).sub.3.6H.sub.2O, FSO.sub.2OOSO.sub.2F, Eu,
acetylcholine, R.sub.4N.sup.+, (R is an alkyl group),
R.sub.4P.sup.+ (R is an alkyl group), R.sub.6As.sup.+ (R is an
alkyl group), and R.sub.3S.sup.+ (R is an alkyl group).
The conducting form of the compounds and materials of the present
invention can be used as an organic "metal" in applications, for
example, but not limited to, charge injection layers and ITO
planarising layers in organic light emitting diode applications,
films for flat panel displays and touch screens, antistatic films,
printed conductive substrates, patterns or tracts in electronic
applications such as printed circuit boards and condensers.
The mono-, oligo- and polyazulenes of the present invention are
useful as optical, electronic and semiconductor materials, in
particular as charge transport materials in field effect
transistors (FETs), e.g., as components of integrated circuitry, ID
tags or TFT applications. Alternatively, they may be used in
organic light emitting diodes (OLEDs) in electroluminescent display
applications or as backlight of, e.g., liquid crystal displays, as
photovoltaics or sensor materials, for electrophotographic
recording, and for other semiconductor applications.
Especially the oligomers and polyazulenes according to the
invention show advantageous solubility properties which allow
production processes using solutions of these compounds. Thus
films, including layers and coatings, may be generated by low cost
production techniques, e.g., spin coating. Suitable solvents or
solvent mixtures comprise alkanes and/or aromatics, especially
their fluorinated derivatives.
The materials of the present invention are useful as optical,
electronic and semiconductor materials, in particular as charge
transport materials in field effect transistors (FETs), as
photovoltaics or sensor materials, for electrophotographic
recording, and for other semiconductor applications. Such FETs,
where an organic semi-conductive material is arranged as a film
between a gate-dielectric and a drain and a source electrode, are
generally known, e.g., from U.S. Pat. No. 5,892,244, WO 00/79617,
U.S. Pat. No. 5,998,804, and from the references cited in the
background and prior art chapter and listed below. Due to the
advantages, like low cost production using the solubility
properties of the compounds according to the invention and thus the
processability of large surfaces, preferred applications of these
FETs are such as integrated circuitry, TFT-displays and security
applications.
In security applications, field effect transistors and other
devices with semi-conductive materials, like transistors or diodes,
may be used for ID tags or security markings to authenticate and
prevent counterfeiting of documents of value like banknotes, credit
cards or ID cards, national ID documents, licenses or any product
with money value, like stamps, tickets, shares, cheques etc.
Alternatively, the mono-, oligo- and polymers according to the
invention may be used in organic light emitting devices or diodes
(OLEDs), e.g., in display applications or as backlight of, e.g.,
liquid crystal displays. Common OLEDs are realized using multilayer
structures. An emission layer is generally sandwiched between one
or more electron-transport and/or hole-transport layers. By
applying an electric voltage electrons and holes as charge carriers
move towards the emission layer where their recombination leads to
the excitation and hence luminescence of the lumophor units
contained in the emission layer. The inventive compounds, materials
and films may be employed in one or more of the charge transport
layers and/or in the emission layer, corresponding to their
electrical and/or optical properties. Furthermore their use within
the emission layer is especially advantageous, if the compounds,
materials and films according to the invention show
electroluminescent properties themselves or comprise
electroluminescent groups or compounds. The selection,
characterization as well as the processing of suitable monomeric,
oligomeric and polymeric compounds or materials for the use in
OLEDs is generally known by a person skilled in the art, see, e.g.,
Meerholz, Synthetic Materials, 111 112, 2000, 31 34, Alcala, J.
Appl. Phys., 88, 2000, 7124 7128 and the literature cited
therein.
According to another use, the inventive compounds, materials or
films, especially those which show photoluminescent properties, may
be employed as materials of light sources, e.g., of display devices
such as described in EP 0 889 350 A1 or by C. Weder et al.,
Science, 279, 1998, 835 837.
The entire disclosure of all applications, patents and
publications, cited above and below, and of corresponding European
Patent application No. 01129216.6., filed Dec. 10, 2001 is hereby
incorporated by reference.
From the foregoing description, one skilled in the art can easily
ascertain the essential characteristics of this invention and,
without departing from the spirit and scope thereof, can make
various changes and modifications of the invention to adapt it to
various usages and conditions.
* * * * *